The present invention relates to compounds of the formula I 
in which
Y is hydrogen, C1-C4alkyl, C1-C4alkoxy, OH, CN, NO2, Si(CH3)3, CF3 or halogen,
Z is a group a) 
xe2x80x83and in which the remaining substituents are defined as follows:
R1 is hydrogen, C1-C4alkyl, C2-C4alkenyl, C2-C4-alkynyl, C3-C6cycloalkyl, phenyl which is unsubstituted or at most trisubstituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, or benzyl which is unsubstituted or at most trisubstituted in the aromatic ring in the same manner or is cyclopropylmethyl, C1-C4haloalkyl, C2-C5alkoxyalkyl, cyanomethyl COxe2x80x94R6, OH, NH2, C1-C4alkylamine or C1-C4alkoxycarbonyl-C1-C2alkyl;
X is oxygen, sulfur or NR5;
R2 is hydrogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C3-C6cycloalkyl, C(O)R6, OH C1-C4alkoxy, NH2 or C1-C4alkylamine;
R5 is hydrogen, C1-C4alkyl, C2-C4alkenyl or C2-C4alkyny;
R6 is hydrogen, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkoxy, C3-C6cycloalkyl, C1-C4alkoxycarbonyl or phenyl which is unsubstituted or at most trisubstituted;
and in which R3 and R4 independently of one another are hydrogen, cyano, C1-C4alkyl, halo-C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C3-C6cycloalkyl, cyclopropylmethyl, C1-C4alkoxy, C2-C5alkoxyalkyl, C1-C4alkoxycarbonyl, C1-C4alkylthio, C2-C5alkylthioalkyl; a ring having not more than 15 ring carbon atoms which can be polymemberd, and is unsubstituted or at most trisubstituted and has 0-3 hetero atoms N, O or S, it being possible for this ring to be bonded via an aliphatic bridge having not more than 4 carbon atoms and/or via either CO, oxygen or sulfur; or
in which R3 and R4 together with the shared carbon atom are a ring or a polymembered ring system having not more than 15 ring carbon atoms which is unsubstituted or at most trisubstituted and has 0-3 hetero atoms N, O or S;
the possible substituents of all these rings mentioned for R3 and R4, either individually or in combination, being selected from amongst C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4haloalkyl, C2-C4haloalkenyl, C2-C4haloalkynyl, C1-C4haloalkoxy, halogen, cyano, cyano-C1-C2alkyl, cyano-C1-C2aloxy, OH, NO2, SCN, thiocyanomethyl, Si(CH3)3, NH2, NH(C1-C4alkyl), N(C1-C4alkyl)2, C1-C4alkoxymethyl, C1-C4alkylcarbonyl, C1-C4alkoxycarbonyl, C1-C4alkoximinomethyl, xe2x80x94CSNH2, xe2x80x94SH, C1-C4alkylthio, C1-C4alkylthiomethyl, C2-C4alkenyloxy, C2-C4alkynyloxy, C2-C4haloalkenyloxy, C1-C4alkylsulfinylmethyl, C1-C4alkylsulfonylmethyl, phenylsulfinylmethyl, phenylsulfonylmethyl, trifluoromethylsulfonyl, C3-C6cycloalkyl; phenyl, benzyl, phenoxy, phenylthio, benzyloxy and benzylthio; it being possible for the last-mentioned aromatic substituents to have not more than three further substituents in the phenyl ring which are selected from amongst halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4haloalkyl, C1-C4haloalkoxy, CN and NO2 and it being possible for two of the substituents, of which there are not more than 3, to form, together with the adjacent substituents, an aliphatic bridge which has not more than 5 members and which has 0-2 oxygen atoms and 0-1 carbonyl group and which can be not more than tetrasubstituted by halogen, C1-C4alkyl, C1-C4alkoxy and/or by a single phenyl group.
In a narrower sense of the meaning the invention refers also to the above-mentioned group of compounds of formula I, wherein R1 is hydrogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alkynyl, C3-C6cycloalkyl; or is phenyl which is unsubstituted or at most trisubstituted by halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio; or is benzyl which is unsubstituted or at most trisubstituted in the aromatic ring in the same manner, and wherein R2 is hydrogen, C1-C4alkyl, C2-C4alkenyl, C2-C4alknyl, C3-C6cycloalkyl, C(O)R6, OH or C1-C4alkoxy.
If asymmetric carbon atoms are present in the compounds of the formula I, the compounds occur in optically active form. On account of the presence of the imino double bond on its own, the compounds in any case occur in the [E]- or [Z]-form. Atropisomerism can also occur. The formula I is intended to include all these possible isomeric formulae and also their mixtures, e.g. racemic mixtures and any desired [E/Z]-mixtures.
The compounds according to the invention have fungicidal properties and are suitable as fungicidal active ingredients in crop protection.
If the compounds I have at least one basic centre, they can form acid addition salts. These are formed, for example, with strong inorganic acids, such as mineral acids, for example sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as C1-C4 alkanecarboxylic acids which are unsubstituted or substituted, for example by halogen, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids, such as C1-C4alkane- or arylsulfonic acids which are unsubstituted or substituted, for example by halogen, for example methane- or p-toluenesulfonic acid. Due to the close relationship between the compounds I in free form and in the form of their salts, they are, analogously, to be understood as meaning, if appropriate, the relevant salts or the free compounds I.
Unless otherwise defined, the general terms used hereinabove and hereinafter are defined as follows.
Alkyl groups on their own or as structural element of other groups are straight-chain or branched, depending on the number of carbon atoms. C1-C4Alkyl is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.
Alkenyl as a group or as structural element of other groups and compounds, such as alkenyloxy, arylalkenyl and heteroarylalkenyl, is either straight-chain, for example ethenyl, propen-1-yl or but-1-en-1-yl, or branched, for example propen-2-yl or but-1-en-2-yl.
Alkynyl as a group or as structural element of other groups and compounds, such as alkynyloxy, is either straight-chain, for example ethynyl, propyn-1-yl or but-1-yn-1-yl, or branched, for example propyn-2-yl or but-1-yn-2-yl.
Cycloalkyl as a group or as structural element of other groups and compounds, such as cycloalkylmethoxy, is, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
Carbocyclic rings on their own or as structural element of other groups, such as aryl-C1-C4alkyl, aryloxy-C1-C4alkyl, arylthio-C1-C4alkyl, arylcarbonyl and aryl-C2-C4alkenyl groups, have, in particular, 6 to 14 C atoms and are, for example, naphthyl, tetrahydronaphthyl, indanyl, fluorenyl, phenanthryl or in particular phenyl. They can be aromatic, partially hydrogenated or completely saturated. One or two benzene rings may be fused to carbocyclic rings.
Rings having hetero atoms, as a group as such and as structural element of other groups and compounds, such as heteroaryl-C1-C4alkyl, heteroaryloxy-C1-C4alkyl, heteroarylthio-C1-C4alkyl, heteroarylcarbonyl and heteroaryl-C2-C4alkenyl groups, have, in particular, 5 to 14 ring members, of which 1 to 3 members are hetero atoms selected from amongst the group oxygen, sulfur and nitrogen. Examples which may be mentioned are benzimidazolyl, benzocumarinyl, benzofuryl, benzothiadiazolyl, benzothiazolyl, benzothienyl, benzoxazolyl, benzoxdiazolyl, quinazolinyl, quinolyl, quinoxalinyl, carbazolyl, dihydrobenzofuryl, ethylenedioxyphenyl, furyl, imidazolyl, indazolyl, indolyl, isoquinolyl, isothiazolyl, isoxazolyl, methylenedioxyphenyl, naphthyridinyl, oxazolyl, phenanthridinyl, phthalazinyl, pteridinyl, purinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyrazolo[3,4-b]pyridyl, pyridyl, pyrimidinyl, pyrrolyl, tetrazolyl, thiadiazolyl, thiazolyl, thienyl, triazinyl and triazolyl.
Preferred heteroaryl radicals R3 and/or R4 are benzofuryl, benzothienyl, quinolyl, quinoxalinyl, dihydrobenzofuryl, ethylenedioxy, furyl, methylenedioxy, pyridyl, pyrimidinyl, pyrrolyl, thiazolyl and thienyl.
One or two benzene rings may be fused to heterocyclic rings.
Halogen is fluorine, chlorine, bromine or iodine. Examples of haloalkyl and haloalkoxy groups are xe2x80x94CH2F, xe2x80x94CHF2, xe2x80x94CF3, xe2x80x94CH2Cl, xe2x80x94CHCl2, xe2x80x94CHCl2, xe2x80x94CCl3, xe2x80x94CCl2CCl3, xe2x80x94CH2Br, xe2x80x94CH2CH2Br, xe2x80x94CHBrCl, xe2x80x94OCHF2, OCF3, OCH2CF3, OCF2CHF2 and OCF2CHFCF3.
One of the preferred groups of the formula I is formed by those compounds in which Z is the group a) in which X is oxygen and R1 is C1-C4alkyl, while R2 is hydrogen, C1-C4alkyl, OH or C1-C4alkoxy.
Preferred amongst these are those compounds in which R1 is methyl and R2 is hydrogen or methyl.
Another preferred group of the formula I is formed by those compounds in which Z is the group a) in which X is sulfur and R1 is methyl or ethyl, while R2 is hydrogen or C1-C4alkyl.
Another preferred group of the formula I is formed by those compounds in which Z is the group a) in which X is sulfur; R1 is methyl, ethyl, allyl, benzyl, cyclopropylmethyl; R2 is hydrogen, C1-C2alkyl; R3 is methyl, methoxy, methylthio or cyclopropyl; and R4 is phenyl which is mono- or di-substituted in 3- and/or 4-position with one or two substituents selected from the group consisting of halogen, methoxy, trifluoromethyl and trifluoromethoxy.
This group will be designated subgroup ICC.
Preferred compounds within the scope of this group ICC are those, wherein R4 is 3-chlorophenyl, 3-bromophenyl, 4-chlorophenyl, 4-bromophenyl, 3-trifluoromethylphenyl, 3-trifluoromethoxyphenyl, 3-fluoro-4-methoxyphenyl or 3-chloro-4-methoxyphenyl.
This group will be designated subgroup Icc.
Another preferred group of the formula I is formed by those compounds in which Z is the group a) in which X is xe2x80x94NR5xe2x80x94 and R5 is hydrogen or C1-C4alkyl, while R1 and R2 independendy are hydrogen or C1-C4alkyl.
Preferred compounds amongst the last-mentioned ones are those in which R1, R2 and R5 independently are hydrogen or methyl.
An important group of compounds is formed by those compounds of the formula I in which the substituents are defined as follows:
Y is hydrogen,
Z is a group a) where X is oxygen or group b),
R1 is C1-C4alkyl
R2 is H, C1-C4alkyl, OH, C1-C4alkoxy
R3 is H, C1-C4alkyl, cyclopropyl, C1-C2alkoxy, C1-C2alkylthio, methoxymethyl, cyano, trifluoromethyl,
R4 is halophenyl having 1 to 2 halogen atoms, mono-C1-C2alkylphenyl, monohalo-mono-(C1-C2alkoxy)phenyl, mono-(C1-C4-alkoxy)phenyl, 3-(halo-C1-C4alkyl)phenyl having 1 to 3 halogen atoms, trifluoromethylphenyl which is substituted by fluorine or chlorine, 3-(halo-C1-C4alkoxy)phenyl having 1 to 6 halogen atoms (in particular fluorine), 3-(C2-C4alkenyloxy)phenyl, 3-(C2-C4alkynyloxy)phenyl, 3-(C3-C6cycloalkylnmethoxy)phenyl, 3-(cyano-C1-C3alkoxy)phenyl, bis(trifluoromethyl)phenyl, tolyl which is substituted by fluorine or chlorine, monocyanophenyl, trifluoromethylphenyl which is substituted by methylthio, or 3-(trimethylsilyl)phenyl, methoxynitrophenyl, 3- or 4-phenoxyphenyl; 3-(methylsulfinylmethyl)- or 3-(methylsulfonylmethyl)phenyl which are unsubstituted or substituted by methoxy; or 3-trifluoromethyl, 4-chlorobenzyl, 3-(trifluoromethyl)phenoxymethyl, 3-trifluoromethylbenzoyl, 2-naphthyl, phenyl which is substituted in the 3- and 4-position by straight-chain C1-C3alkylenedioxy (in particular methylenedioxy, ethylenedioxy, 2,2-difluoromethylenedioxy, 2-methoxymethylenedioxy), dihydrobenzofur-5-yl, 2-thienyl, benzofur-2-yl, 2-furyl, 5-chloro- or 5-bromothien-2-yl, 3-methylbenzo[b]thien-2-yl, 1-methylpyrrol-2-yl, 2-thiazolyl, 2-pyridyl which is unsubstituted or substituted by halogen or trifluoromethyl, or 6- or 7-quinolinyl, 6-quinoxalinyl, 2-pyrimidinyl which is mono- to disubstituted by halogen, methyl, trifluoromethyl, cyclopropyl, C1-C3alkoxy or methylthio; 4-(2,6-dimethylmorpholinyl); or R3 and R4 together are a 5,6-dihydro-2H-1,4-thiazine ring which is substituted in the 3-position by substituted phenyl, or R3 and R4 together are a cyclopentane or tetrahydropyran ring to which an unsubstituted or halogen-substituted benzene ring is fused.
This group will be designated subgroup IDD.
Preferred compounds within the scope of this group IDD are those in which the substituents are defined as follows:
R1 is C1-C2alkyl
R2 is H, C1-C2alkyl, OH, C1-C4alkoxy
R3 is H, C1-C2alkyl, cyclopropyl, methoxy, methylthio, methoxymethyl, cyano, trifluoromethyl,
R4 is monohalophenyl, dihalophenyl, mono-C1-C2alkylphenyl, mono-C1-C2alkoxyphenyl, 2-naphthyl, 3,4-methylenedioxyphenyl, 3,4-ethylenedioxyphenyl, 2,2-difluoro-5-benzodioxolyl, 2-methoxy-5-benzodioxolyl, 3-(fluoro-C1-C2alkoxy)phenyl having 1-3 fluorine atoms, 3-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl, 4-fluoro-3-trifluoromethylphenyl, 3-fluoro-5-trifluoromethylphenyl, 4-chloro-3-trifluoromethylphenyl, 4-chloro-3-tolyl, monocyanophenyl, 3-cyanomethoxyphenyl, 2-methylthio-5xe2x80x2-trifluoromethylphenyl, 4-methoxy-3-nitrophenyl, 3- or 4-phenoxyphenyl, 3-methylsulfinylmethyl-4-methoxyphenyl, 3-methylsulfonyl-4-methoxyphenyl, 3-(prop-1-en-3-yloxy)phenyl, 3-(prop-1-yn-3-yloxy)phenyl, 3-(cyclopropylmethoxy)phenyl, 2,3-dihydrobenzofur-5-yl, 3-trifluoromethyl, 4-chlorobenzyl, 3-trifluoromethylphenoxymethyl, 2-pyridyl, 6-bromo-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 6- or 7-quinolinyl, 6-quinoxalinyl, 2-thienyl, 5-chloro- or bromothien-2-yl, 3-methylbenzo[b]thien-2-yl, 2-furyl benzo[b]fur-2-yl, 1-methylpyrrol-2-yl, 2-thiazolyl, 4-(2,6-dimethylmorpholinyl); or R3 and R4 together are a 5,6-dihydro-2H-1,4-thiazine ring which is substituted in the 3-position by mono- or dihalophenyl, methoxyphenyl, trifluoromethylphenyl, phenoxy or 3,4-methylenedioxyphenyl, or R3 and R4 together are a cyclopentane or tetrahydropyran ring to which an unsubstituted or fluorine-substituted benzene ring is fused.
This group will be designated subgroup IEE. Preferred compounds within this group are those defined as follows:
R1 is C1-C2alkyl,
R2 is H, methyl,
R3 is methyl, methoxy, ethyl, methylthio, cyclopropyl,
R4 is 3-halophenyl, 4-halophenyl, 3-trifluoromethylphenyl, 3-(C1-C4haloethoxy)phenyl, 4-fluoro-3-trifluoromethylphenyl, 4-tolyl, 3,4-methylenedioxyphenyl, or 3,4-ethylenedioxyphenyl (=subgroup Iee).
Another preferred subgroup within the scope of IDD is that wherein R1 is C1-C2alkyl, R2 is hydrogen, C1-C2alkyl, OH, C1-C4alkoxy, R3 is hydrogen, C1-C2alkyl, cyclopropyl, methoxy, methylthio, methoxymethyl, cyano, trifluoromethyl and R4 is monohalo-monomethoxyphenyl. (=Subgroup Idd).
Among Idd important compounds are those wherein R4 is 3-halo-4-methoxyphenyl. Further preferred compounds within the group Idd are those defined as follows: R1 is C1-C2alkyl, R2 is hydrogen or methyl, R3 is methyl, methoxy, ethyl, methylthio, cyclopropyl; and R4 is 3-halo-4-methoxyphenyl.
A specific group within the scope of the formula I is formed by compounds which are defined as follows:
Z is the group a) where X is oxygen, sulfur, xe2x80x94NHxe2x80x94 or xe2x80x94NCH3,
R1 is C1-C2alkyl,
R2 is H, methyl,
R3 is methyl, cyclopropyl and
R4 is 3-chlorophenyl, 3-trifluoromethylphenyl, 3-trifluoromethoxyphenyl, 4-chlorophenyl.
Another specific group within the scope of the formula I is formed by compounds which are defined as follows:
Z is the group a) where X is oxygen, sulfur, xe2x80x94NHxe2x80x94 or xe2x80x94NCH3,
R1 is C1-C2alkyl,
R2 is H, methyl,
R3 is methyl, cyclopropyl and
R4 is 3-fluor-4-methoxyphenyl.
The invention furthermore relates to a process for the preparation of the compounds according to the invention, to pesticidal, especially microbicidal compositions comprising such compounds as active ingredients, and to the use of such compounds and compositions for preferably controlling phytopathogenic fungi and for preventing attack by fungi.
The iminoethers, iminothioethers and amidines of the general formula 
in which R1, R2, R3, R4, X and Y are as defined above can be prepared analogously to known methods as they are indicated, for example, in the following references:
xe2x80x9cThe Chemistry of amidines and imidatesxe2x80x9d ed. S. Patai, John Wiley and Sons, Vol. 1, 1974 and Vol. 2, 1991, in each case Chapter 7 and 9;
Houben-Weyl xe2x80x9cMethoden der organischen Chemiexe2x80x9d [Methods in Organic Chemistry], Vol. 8, 1975 and E5, 1985.
For example, imino(thio)ethers of the general formula II in which R2 is hydrogen and X is oxygen or sulfur and in which R1, R3 and R4 are as defined above can be prepared in accordance with the following equation*
*The following formulae III to XI are to be understood as also comprising the phenylsubstituent Y. 
The nitriles of the general formula III in which R3 and R4 are as defined above are reacted with a (thio)alcoholate R1Xxe2x8ax96 at a temperature between 20xc2x0 C. and 150xc2x0 C., if appropriate in an autoclave under pressure. It is expedient to use the corresponding (thio)alcohol or inert organic solvents, for example diethyl ether, dichloromethane, dimethylformamide, tetrahydrofuran or toluene, as diluent.
Furthermore, imino(thio)ethers of the general formula II in which R1 is C1-C4alkyl and X is oxygen or sulfur and in which R2, R3 and R4 are as defined above can be prepared from the (thio)amides of the general formula IV 
in which X is oxygen or sulfur and in which R2, R3 and R4 are as defined above. To this end, the (thio)amides are reacted with a trialkyloxonium tetrafluoroborate at a temperature from 0xc2x0 C. to 50xc2x0 C. in a suitable solvent, for example dichloromethane, chloroform or toluene.
Iminothioethers of the general formula II in which X is sulfur and in which R1, R2, R3 and R4 are as defined above can also be prepared from the thioamides of the general formula V 
in which R2, R3 and R4 are as defined above. To this end, the thioamides are reacted with halides in the presence of bases, for example potassium carbonate, potassium hydroxide, sodium ethylate and sodium hydride, in a suitable solvent, for example diethyl ether, tetrahydrofuran, dimethylforamide, dimethyl sulfoxide or toluene, at a temperature between 10xc2x0 C. and 100xc2x0 C.
Imino(thio)ethers of the general formula II in which R2 is defined as xe2x80x94C(O)R5 and in which R3 and R4 are as defined above can be prepared from the corresponding N-unsubstituted imino(thio)ethers by acylation. 
The reaction is carried out in the customary manner using the corresponding acid halides (in particular chlorides and bromides) or chloroformates in the presence of a base or a base mixture composed of triethylamine, pyridine, 4-dimethylaminopyridine and the like in a suitable organic solvent, for example dichloromethane, ethyl acetate, tetrahydrofuran or toluene, in a temperature range between 0xc2x0 C. and 50xc2x0 C.
In a further embodiment, imino(thio)ethers and amidines of the general formula II in which X, R1, R2, R3 and R4 are as defined above can be obtained starting from chlorides of the general formula VI in which R2, R3 and R4 are as defined above 
by reaction with (thio)alcoholates or amines in a suitable organic solvent, for example diethyl ether, dichlomomethane, dimethylformamide, tetrahydrofuran or toluene, at a temperature between xe2x88x9220xc2x0 C. and +80xc2x0 C. The chlorides, in turn, are accessible from the corresponding (thio)amides, for example by reaction with phosphorus oxychloride, thionyl chloride or triphenylphosphine/carbon tetrachloride. See, in this context, C. Ferri, Reaktionen der Organischen Synthese [Reactions in Organic Synthesis]; p. 564, G. Thieme Verlag, Stuttgart 1978.
Amidines of the general formula II in which X is NR1 and R1, R2, R3 and R4 are as defined above can furthermore be prepared from the iminoethers of the general formula VII in which R1, R2, R3 and R4 are as defined above 
by reaction with a primary or second amine in a suitable solvent, for example dichloromethane, dioxane, dimethylformamide or toluene, at a temperature between xe2x88x9220xc2x0 C. and +60xc2x0 C.
Thioamides of the general formula Ib can be prepared from the corresponding amides by xe2x80x9csulfur treatmentxe2x80x9d. Substances which can be used for this reaction are, for example, PS5 or Lawesson reagents (see, in this context, Cava and Lawesson, Tetrahedron 41, 5061 [1985]) 
Thioamides of the general formula Ibxe2x80x2 can furthermore be obtained from the nitriles of the formula III by an addition reaction with hydrogen sulfide in the presence of a base, for example potassium carbonate, potassium hydroxide or triethylamine, in a suitable solvent, for example dichloromethane, dimethylformamide, chloroform, carbon tetrachloride or tetrahydrofuran. They can, however, also be obtained by the reaction of the nitriles of the formula III with bis(trimethylsilyl)sulfide and sodium methylate (according to P. Y. Lin et al., Synthesis 1992 (12), p. 1219). 
The nitriles of the general formula III can be prepared from compounds of the general formula IX in which U is a leaving group, 
by reaction with oximes of the general formula X in which R3 and R4 are as defined above. The leaving group U is preferably to be understood as meaning chlorine, bromine, iodine, mesyloxy or tosyloxy. The reaction is carried out, for example, in the presence of a base, such as potassium carbonate, potassium hydroxide, sodium hydride or sodium methylate, in a suitable organic solvent, for example acetone, acetonitrile, dimethylformamide or in tetrahydrofuran, at temperatures between xe2x88x9220xc2x0 C. and +80xc2x0 C.
The reaction can also be carried out in a suitable two-phase system (for example water and dichloromethane) in the presence of a phase-transfer catalyst, for example benzyltrimethylammonium chloride.
Important compounds of the formula IX are those in which U is chlorine or bromine. They can be prepared from xcex1-hydroximino-o-tolylacetonitrile, which is known, by O-methylation by means of dimethyl sulfate or methyl iodide in the presence of a base, followed by halogenation, for example by means of N-bromo or N-chlorosuccinimide in boiling carbon tetrachloride. 
In a further embodiment, the nitriles of the formula III can be prepared by dehydrating the amides of the general formula XI 
in which R3 and R4 are as defined above. The reaction is carried out for example using trifluoroacetic anhydride in the presence of bases, for example pyridine, triethylamine or potassium carbonate, or by means of the system tertiary phosphane/CCl4 in the presence of tertiary nitrogen bases (see, in this context, R. Appel in Angew. Chem. 87, 869 (1975).
The oximes of the formula X used can be prepared by methods known per se, for example from the corresponding ketones by means of hydroxylamine or a salt thereof, in the presence of a base, for example pyridine. Other methods can be found in Houben-Weyl, Vol. 10/4, p. 3-308 (1968).
Amides of the formula VIII have been disclosed in Patent Publications EP-A-463 488 and WO 92/13830 and can be prepared by the processes described therein.
The invention also relates to the novel imidoyl chlorides of the formula VI in which R2, R3 and R4 are as defined above.
It has now been found that compounds of the formula I, which are distinguished from benzyl oxime ethers from the literature by, inter alia, the novel structural element of the formula CH3Oxe2x80x94Nxe2x95x90C(Z)xe2x80x94, have a microbicidal spectrum for controlling phytopathogenic microorganisms, in particular fungi, which is particularly useful for practical requirements. They have very advantageous curative, preventive and, in particular, systemic properties and can be used for the protection of a large number of crop plants. Using the active ingredients of the formula I, the pests which occur on plants or parts of plants (fruits, flowers, foliage, stalks, tubers, roots) of various crops of useful plants can be controlled or destroyed and even parts of plants which are formed at a later stage of growth remain free from phytopathogenic microorganisms.
The compounds of the formula I can furthermore be used as seed-dressing agents for the treatment of seeds (fruits, tubers, grains) and plant cuttings or other propagation material for the protection against fungal infections and against soil-borne phytopathogenic fungi.
Compounds of the formula I are active for example against phytopathogenic fungi which belong to the following classes: Fungi imperfecti (in particular Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora, Cercosporella and Alternaria); Basidiomycetes (for example Rhizoctonia, Hemileia, Puccinia). Moreover, they are active against the class of the Ascomycetes (for example Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula), but mainly also against the class of the Oomycetes (for example Phytophthora, Peronospora, Bremia, Pythium, Plasmopara).
Target crops for the crop-protecting use disclosed herein are, within the scope of this invention, for example the following types of plants: cereals (wheat, barley, rye, oats, triticale, rice, maize, sorghum and related species); beet (sugar and fodder beet); pome fruit, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, gooseberries, raspberries and blackberries); pulses (beans, lentils, peas, soya beans); oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor, cocoa, groundnuts); cucurbits (pumpkin, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, tangerines); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, bell pepper); the laurel family (avocado, cinnamon, camphor), or plants such as tobacco, nuts, coffee, sugarcane, tea, pepper and other spice plants, grapevine, hops, eggplants, the banana family, latex plants and ornamentals.
Active ingredients of the formula I are customarily used in the form of combinations and can be applied to the plant or the area to be treated simultaneously or in succession with other active ingredients. These other active ingredients can be fertilizers, trace element mediators or other preparations which have an effect on plant growth. Selective herbicides and insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of a plurality of these preparations, with or without other carriers conventionally used in the art of formulation, surfactants or other application-enhancing additives, can also be used.
Suitable carriers and additives can be solid or liquid and are those substances which are expedient in the art of formulation, for example natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
The following are possible as solvents: aromatic hydrocarbons, preferably the fractions C8 to C12, for example xylene mixtues or substituted naphthalenes, phthalic esters, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols as well as their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and also epoxidized or unepoxidizrd vegetable oils, such as epoxidized coconut oil or soya oil; or water.
Solid carriers which are generally used, for example for dusts and dispersible powders, are ground natural rocks, such as calcite, talc, kaolin, montmorillonite or attapulgite.
Particularly expedient application-enhancing additives which may result in a greatly reduced rate of application, are, moreover, natural (animal or vegetable) or synthetic phospholipids from the series of the cephalins and lecithins, which can be obtained from, for example, soya beans.
Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated. Surfactants are also to be understood as meaning mixtures of surfactants.
Suitable anionic surfactants can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
Soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts of higher fatty acids (C10-C22), for example the sodium or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained from, for example, coconut oil or tallow oil. Mention must also be made of the fatty acid methyl taurinates.
Possible non-ionic surfactants are polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can have 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
Examples of non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
Moreover, fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate, are also suitable.
The cationic surfactants are mainly quaternary ammonium salts which have, as N-substituent, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower, halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals.
The anionic, non-ionic or cationic surfactants conventionally used in the art of formulation are known to the expert or can be found in the relevant specialist literature:
xe2x80x9cMc Cutcheon""s Detergents and Emulsifiers Annualxe2x80x9d, Mc Publishing Corp., Glen Rock, N.J., 1988.
M. and J. Ash, xe2x80x9cEncyclopedia of Surfactantsxe2x80x9d, Vol. I-III, Chemical Publishing Co., New York, 1980-1981.
Dr. Helmut Stache xe2x80x9cTensid-Taschenbuchxe2x80x9d [Surfactants Guide], Carl Hanser Verlag, Munich/Vienna 1981.
As a rule, the agrochemical preparations comprise 0.1 to 99%, in particular 0.1 to 95%, of active ingredient of the formula I, 99.9 to 1%, in particular 99.9 to 5%, of a solid or liquid additive, and 0 to 25%, in particular 0.1 to 25%, of a surfactant.
While concentrated compositions are more preferred as commercial products, the end user will, as a rule, use dilute compositions.
The compositions can also comprise other additives, such as stabilizers, antifoams, viscosity regulators, binders, tackifiers and fertilizers or other active ingredients for achieving specific effects.
The formulations, i.e. the compositions, preparations or combinations comprising the active ingredient of the formula I and, if appropriate a solid or liquid additive, are produced in a known manner, for example by intimately mixing and/or grinding the active ingredient with an extender, for example a solvent (mixture), a solid carrier material and, if appropriate, surface-active compounds (surfactants).
A preferred process for applying an active ingredient of the formula I, or an agrochemical composition comprising at least one of these active ingredients, is applying to the foliage (foliar application). Frequency of application and rate of application both depend on the danger of attack by the pathogen in question. However, the active ingredients of the formula I can also reach the plant via the soil through the root system (systemic action) by drenching the locus of the plant with a liquid composition or by incorporating the substances into the soil in solid form, for example in the form of granules (soil application). In the case of paddy rice, such granules can be metered out into the flooded rice field. Alternatively, the compounds of the formula I can be applied to seed kernels (coating), either by soaking the kernels in a liquid preparation of the active ingredient or by coating them with a solid preparation. In principle, any type of plant propagation material can be protected using compounds of the formula I, for example seeds, roots or stalks.
The compounds of the formula I are used as pure compounds or, preferably, together with the auxiliaries conventionally used in the art of formulation. To this end, they are advantageously processed in the known manner, for example to give emulsifiable concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and encapsulations, for example in polymeric substances. The methods of application, such as spraying, atomizing, dusting, scattering, brushing on or pouring, as well as the nature of the compositions are selected to suit the intended aims and the prevailing circumstances. Favourable rates of application are, generally, 5 g to 2 kg of active ingredient (AI) per ha, preferably 25 g to 800 g of AI/ha and, particularly preferably, 50 g to 400 g of AI/ha. When used as seed-dressing products, dosage rates of 0.001 g to 1.0 g of active ingredient are advantageously used per kg of seeds.